DE1125926B - Process for converting oxygen- or sulfur-containing organoaluminum compounds into oxygen- or sulfur-containing aluminum compounds which contain other hydrocarbon radicals - Google Patents

Description

It is known that aluminum trialkyls in the presence of olefins counteract the hydrocarbon content exchange the constituents of the acting olefins, the originally present Hydrocarbon radicals corresponding olefins are split off. Such an exchange occurs frequently spontaneously, but can also be triggered by certain catalysts, e.g. B. nickel, are accelerated. Acquaintance Examples of such a reaction are as follows:

If you boil aluminum triisobutyl with 2-ethylhexene (l), so isobutylene splits off, and aluminum tri- (2-ethyl-hexyl) is formed quantitatively:

Al (C ₄ H ₉ ) ₃ + 3 H ₂ C = C (C ₂ H ₅ ) C ₄ H ₉ _►
iso

- » Al [- CH ₁ - CH (C ₂ H ₅ ) C ₄ H ₉ ] S + 3 (CH ₃ ) ₂ C = CH ₂

This elimination of olefins takes place spontaneously at the boiling point of the olefin of about 120.degree.

Treating a higher aluminum trialkyl with straight-chain radicals with ethylene in the presence of some colloidal nickel, aluminum triethyl is formed, and the remains of aluminum are split off in the form of straight-chain α-olefins:

Al (C _n H _{2 n +1} ) ₃ + 3 C ₂ H ₄ -> Al (C ₂ H ₅ ) ₃ + 3 C _n H _2n

In general, mixtures of aluminum hydrocarbons, in particular aluminum trialkylene, equilibrium systems with olefins are of the following type:

Al (alkyl I) ₃ + 3 olefin II = * = Al (alkyl H) ₃ + 3 olefin I

it is possible to accelerate the establishment of equilibrium by adding colloidal nickel. Depending on the individual reaction conditions, it is possible to shift the equilibria in one direction or the other. That is, if the olefin II is used in excess, predominantly Al (alkyl H) _{3 is} formed in the end product; if the olefin I is in excess, the reverse is true. If one of the two olefins involved in the establishment of the equilibrium is more volatile than the other, then by removing this more volatile olefin one can usually obtain the aluminum trialkyl with the alkyl radicals corresponding to the less volatile olefin as the final state. If the elimination of higher olefins from aluminum trialkylene with ethylene has been described above, this referred to experiments with ethylene in excess. It is of course just as possible if one does not use an excess of ethylene and takes care that the ethylene lau process for the conversion

of oxygen or sulfur-containing

Organoaluminum compounds in oxygen

or sulfur-containing aluminum compounds, the other hydrocarbon radicals contain

Applicant:

Dr. Dr. eh Karl Ziegler,
Mülheim / Ruhr, Kaiser-Wilhelm-Platz 1

Dr. Dr. e. H. Karl Ziegler,

Dr. Roland Koster, Mülheim / Ruhr,

and Dr. Wolf-Rainer Kroll, Witten-Annen,

have been named as inventors

fend can escape, also vice versa from aluminum triethyl and higher olefins to produce higher aluminum alkyls and ethylene.

These conversion possibilities of the aluminum trialkyls can, when suitably combined with others Reactions are technically exploited in the most varied of ways. It is also known that one aluminum hydrocarbons according to the following formula with ethylene in higher homologues can convert:

R (C ₂ H ₄ X _n R

Al ^ -R + (m + η + O) C ₂ H ₄ - ^ Al ζ- (C ₂ H ₄ ) "R
R (C ₂ H ₄ ) ,, R

R stands for hydrocarbon radicals which can be identical or different from one another.

The reaction is suitable, for example, aluminum triethyl to a statistical mixture of higher aluminum trialkyls, with the average Molecular weight of these higher aluminum trialkyls from that applied per aluminum atom Number of moles of ethylene depends. The higher aluminum alkyls prepared in this way can used as intermediates on the way to other valuable straight-chain compounds

209 520/463

be e.g. B. they supply hydrocarbons through hydrolysis, primary fatty alcohols through oxidation and subsequent hydrolysis.

In this build-up reaction of aluminum hydrocarbons with ethylene, one can under certain circumstances also use organoaluminum compounds in which a valence is bonded to hydrogen is. When using such a compound, an ethylene is first attached to the reaction Aluminum-hydrogen bond adds, so that in turn an aluminum compound is formed contains the three valences of aluminum bonded to the carbon.

A special feature of the reactions described above is that they only work with such compounds are possible in which all three valences of aluminum are bonded to carbon. Aluminum compounds, in which only two valences of aluminum are bonded to carbon and the third valence bonded to any other atom Y will show upon exposure to Olefins do not have this mutual olefin exchange, not even in the presence of nickel. You can z. B. Boil monomethoxyaluminum diisobutyl with 2-ethyl-hexen- (l) for hours without isobutylene escaping. The various technical possibilities that result from the olefin-alkyl exchange, So far, therefore, could not be transferred to aluminum compounds in which only two or even only erne valence is bound to carbon. It is just as impossible to attach such substances to ethylene with formation of higher homologous compounds of the general formula

Y-Al [(C ₂ H ₄ ) _n R] ₂

in which R is any hydrocarbon radical.

It has now been found that reactions of organic aluminum compounds with olefins can be achieved also with organoaluminum compounds of the general formula

XW [Y-AlR ₂ L

in which X is any monovalent or polyvalent hydrocarbon radical, η is the valence of the radical X, Y is oxygen or sulfur and R is any hydrocarbon radical which does not contain any unsaturated bond on the carbon atom bonded to aluminum, preferably an aliphatic or aromatic, substituted or unsubstituted hydrocarbon radical , means, can be achieved when working in the presence of aluminum compounds as catalysts containing three valences bonded to carbon,. or dialkylaluminum hydrides or aluminum hydrides are used instead.

In this way it is possible to use oxygen- or sulfur-containing organoaluminum compounds in oxygen- or sulfur-containing aluminum compounds that contain other hydrocarbon residues, to convert and optionally to win olefins.

The radical X — Y in the organoaluminum starting compounds can, for. B. the remainder of any alcohol, phenol, naphthol or their derivatives substituted by alkyls in the benzene nucleus. The radicals X and R can be aliphatic, isocylic, hydroaromatic, mixed aliphatic-iso. cyclic, mixed hydroaromatic, substituted or unsubstituted aromatic, mixed aliphatic-aromatic, mixed aromatic-hydroaromatic hydrocarbon radicals. The process according to the invention enables higher organoaluminum compounds to be built up by reacting compounds of the general formula XYAlR _{2 with ethylene.} If compounds of the general formula are used

XW [Y-AiIy _n

in the presence of such catalysts with ethylene at pressures above 15 atm, preferably at temperatures between 90 and 170 ° C., in particular 120 and 150 ° C., then essentially higher homologs of the organoaluminum starting compound are obtained. By increasing the reaction ^{temperature to above 170 °} C., olefins can, if desired, be split off from the organoaluminum compounds formed.

According to another process modification, aluminum compounds can first be used general formula

XW [Y-AlR ₈ I,

in which at least one radical R is a radical higher than C ₂ H ₅ , react with ethylene, for example under normal pressure, and then receive olefins other than ethylene in addition to lower or higher homologues of the starting materials.

Optionally, according to the invention, a higher organoaluminum compound can also be used initially build up with the help of ethylene and then in the presence of nickel a displacement of olefins from reach the reaction mixture.

For the reaction of higher homoigenes of the aluminum organisehen The starting compound can of course also be used in place of ethylene, higher olefins. One then receives as an end product besides a lower or higher homologue of the starting compound

the olefin corresponding to the radical R.

The catalysts suitable according to the invention do not work when aluminum compounds of the general formula (XY) _{2 AlR are used.} This is due to the fact that, for example, between an aluminum _{trialkyl and a compound of the type (XY) 2} AlR always a reaction according to

(XY) ₂ AlR + AIR ₃ = 2XYAlR ₂

is possible. The aluminum trialkyl thus does not remain as such in the mixture with the compounds of the type (XY) ₂ AlR, and it can then also not act as a catalyst. Only when the added amount of the real aluminum trialkyl exceeds the equivalent amount is the reaction with olefins possible, but then one can no longer speak of small amounts of the aluminum trialkyl, and the reaction products, e.g. B. with ethylene, would also no longer the construction

(XY) ₂ Al (C ₂ H ₄ ) _n R, but they would have according to XYA1 [(C ₂ H ₄ ) "R] ₂

If, on the other hand, according to the invention, for. B. one Mixture of Methoxydüsobutylaluminium and 2-Äthylen-Hexen- (l) for a mutual exchange of substances between the hydrocarbon radicals of the aluminum compounds of the general formula 5 XYAlR., And a few percent "of any aluminum alkyl" added to the olefin used, so the isobutylene development starts immediately, and the reaction goes, provided that there is enough 2-ethyl-hexene (l) is present until all of the isobutylene is driven off and the aluminum apart from the small amount of catalyst, as methoxy-aluminum-di- [2-ethyl-hexyl- (l)] is present.

Using the trick just described, it is possible to convert the compounds of the XYAlR ₂ type through the action of olefins in exactly the same extent and with the same diversity into other substances of the same type, but with modified alkyl groups, as was previously only known for such aluminum compounds containing all three valences bound to carbon. This possibility is of particular technical importance in connection with the synthesis of higher straight-chain aliphatic compounds from ethylene. According to the prior art, you could have such compounds, for. B. produce higher α-olefins according to the following multistage process:

First stage:

Structure of the higher aluminum trialkyls from a lower aluminum trialkyl, e.g. B. aluminum triethyl, and ethylene:

A1 (C ₂ H ₅ ) ₃ + 3 nC ₂ H ₄ - ^ Al [(C ₂ H ₄ X, C ₂ H ₅ ] ₃

Second step:

Displacement of the higher olefins from the aluminum trialkyl formed with ethylene in the presence of nickel:

Al [(C ₂ H ₄ X, C ₂ H ₅ J ₃ + 3C ₂ H ₄ ^ - * ■ A1 (C ₂ H ₅ ) ₃ + 3 H ₂ C = CH (C ₂ H ₄ ) ^ ₁ C ₂ H ₅

As is well known, η only has the meaning of an average value, and in fact a mixture of different olefins with aluminum triethyl is formed in this second stage.

For the second stage, essentially two embodiments have been proposed so far: the first works with colloidal nickel as a catalyst for displacement, and then the reaction goes very quickly, but a nickel-containing reaction product is obtained. The second works with a solid arranged, lumpy nickel contact, you get a nickel-free reaction product, but the The reaction rate is naturally much lower than with colloidal nickel. Do you want an industrial synthesis of olefins on a repeated execution of these two reaction stages found, the problem arises that the aluminum triethyl formed back from the olefins must separate in order to be able to return it to the first reaction stage. This is technical not that easy, because z. B. decene and dodecene have similar boiling points as aluminum triethyl and hence the complete separation of these two particularly important olefins from the aluminum triethyl is particularly difficult. In addition, it interferes with the attempt to separate the components by distillation the reaction mixture, provided that colloidal nickel was used in the second stage, the presence of this nickel is quite significant, because it also causes the regression of higher aluminum alkyls from aluminum triethyl catalyzed with elimination of ethylene. For these reasons, the work-up was the reaction products in the described olefin synthesis from ethylene is technically difficult and Problem that has not yet been completely satisfactorily solved.

With the method according to the invention, these difficulties have been eliminated in one fell swoop. According to the invention, one can use the aluminum compounds suitable for the above reaction the general formula

X YAl [(C ₂ H ₄ X ₁ R] ₂

build up the three valences of carbon when working in the presence of aluminum compounds bound included. These compounds catalyze the "displacement reaction" when you are in Presence of nickel works. You can therefore use the reaction products of the first process stage Add a little colloidal nickel and treat it with ethylene, resulting in mixtures as end products of few true organoaluminum compounds (the catalysts) with a lot of the compound

XYA1 (C ₂ H ₅ ) ₂

and the desired olefins of the general formula

H ₂ C = CH (C ₂ H ₄ X _1-1 C ₂ H ₅

35 in which η means an integer. If the second stage is treated with an olefin other than ethylene, ζ. B. propylene or butene- (l), the compound XY Al (C ₃ H ₇ ) ₂ or XYA1 (C ₄ H ₉ ) ₂ is formed in addition to the olefin.

It is very easy to arrange that the separation of such mixtures into their components no longer poses any difficulties. First, through a suitable choice of X, the boiling point of XYAlR _{2 can be selected to be} higher than the boiling point of the highest-boiling olefin (or possibly lower than the boiling point of the lowest-boiling olefin if the build-up is very extensive). In addition, before distilling, the catalyst fraction can be rendered ineffective by destroying it by adding a little aluminum alcoholate or some other suitable substance. One makes use of the following reaction options, for example:

2AlR ₃ + Al (OR) ₃ -> 3ROAlR ₂

or more generally

Al (YX) ₃ + 2AlR ₃ - »- 3XYAlR ₂ ⁰ or else

(XY) ₂ AlR + AlR ₃ -> 2XYAlR ₂

Other ways of inactivating the Ka-6 ·; catalysts make use of the fact that aluminum trialkyls react with many reagents only with the first Al — C valence, converting into compounds of the type XYAlR ₂ .

For example, aluminum triethyl reacts with carbon dioxide in the following way:

3A1 (C ₂ H ₆ ) ₃ + CO ₂ -> (C ₂ H ₅ ) _S C-O-A1 (C ₂ H ₅ ) ₂ + (C ₂ H ₅ ) ₂ A1-O-Al (C ₂ H ₅ ),

with acetone according to

A1 (C ₂ H ₅ ) ₃ + (CH ₃ ) ₂ C = O _► (CHy ₈ (C ₈ H ₆ ) COAl (C ₈ Hj) ₈

One can thus also achieve this simply by introducing aluminum groups into di- or polyvalent Al-CO ₂ or adding carbonyl compounds into alcohols, mercaptans or phenols. If an amount equivalent to the catalysts is inactive, compounds like four are obtained. There are also substances with free active ίο ω \ ir \ mn \ η a.it>

Hydrogen atoms, such as alcohols, thioalcohols, K ₂ Ai-υ - ^ «^" - u-aik ₂ (n> iy

Carboxylic acids, suitable, also aluminum salts of the _ / * '"-

Carboxylic acids. 1 mole of alcohol or ^R 2 ^{inactivates A1} ° ( ] ° ^A1R 2

Thioalcohol: 1 mole, 1 mole carboxylic acid: 3 moles and
1 equivalent of the salt: 2 moles of aluminum trialkyl. At 15
this type of inactivation, however, takes CH ₃ —C (CH ₂ —O —- A1R ₂ ) ₃

Accept that valuable Al — C bonds are lost and / or other substances of the type XY Al R ₂ C [CH ₂ —O — AlR ₂ I ₄ are formed than the starting compounds used. and the like.

Incidentally, a convenient method is a 20 The combination of reactions just given The method according to the invention is suitable for the method according to the invention by making coal, apparently one of the most important uses of this Dioxyd initiates in aluminum trialkyls. As well as in the method according to the invention. Reaction mixture the real aluminum trialkyl in The catalytic effect of the inventively

has become inactive in this way without suitable catalysts, preferably aluminum. These great advantages over my formula XYAlR ₂ with ethylene, expediently state of the art, can be achieved solely by the fact that under pressure, at temperatures between 90 and one during the ongoing production of olefins 30 250 ° C, expediently between 90 and 170 ° C, insbeaus ethylene, the small respectively as catalyst loading but sondere, heated from 120 to 15O ⁰ C. The required amount of real organoaluminum very small amounts of catalyst is sufficient, but the natural bond is constantly being lost. However, since the rate of the reaction can be managed with the Karingen amount of catalyst, you can reduce the amount of catalyst. Sufficient speeds can take this into account. In addition, in 35 one can use 1 to 5 "/" organoaluminum associations technical processes in which certain compounds are achieved, with which, however, neither a smaller auxiliary substance, here the aluminum compound of the type nor larger amounts of catalyst, can be excluded XYAlR ₂ , anyway with certain losses are supposed to. In addition, the necessary amount depends on this auxiliary material. It is easy to add catalysts and the purity of the provided that one avoids the addition of the catalyst and ethylene. Certain impurities can be deactivated before distillation by ethylene, such as CO ₂ or acetylene, react with a suitable choice of the catalyst itself and the deactivating aluminum trivial added as catalysts so that they alkylene together and make them ineffective. Therefore it can happen just the necessary supplement of the auxiliary that the reaction according to the invention cause substance. 45 comes to a standstill after a certain period of time. In

To illustrate this with an example, one has such cases, the reaction can be repeated Phenoxyaluminum diethyl, for example, is used as an auxiliary additive of some organoaluminum compound, triethyl aluminum as a catalyst, it will restart gene. It is in the spirit of this one can easily see the deactivation of the catalyst, considerations that are necessary either with aluminum phenolate or with 50 agile amount of the catalyst according to the pure di (phenoxy) aluminum ethyl carry out, whereby the degree of the ethylene has to be judged. then in the course of the deactivation additional men- The amount of the invention to the reaction

gene of the auxiliary substance Pheoxyaluminiumdiäthyl formed bringing ethylene is practically unlimited. Man so that the losses are balanced. can as well with a few moles of ethylene

All 55 reaction products per mole of aluminum compound can be obtained from phenoxydiethylaluminum Distill off olefins up to the hexadecone smoothly, with obtained the still fairly low molecular weight alkyl naphthyloxydiethylaluminum if this succeeds with still remnants - z. B. when talking about ethylaluminum-Verhöhermolekularen Olefins. In addition, compounds show connections, butyl, hexyl or fertilizers of the type octyl residues - contain, as well as with more ethylene

XYAl (CH) ₁ , 60 substances with dodecyl, tetradecyl, hexadecyl, octa-

⁵² decyl etc. residues on the aluminum. If you increase the

often a good ability to crystallize. This still applies to amount of ethylene, so you get z. B. for the two aryloxydiethyl substances just mentioned, finally, substances with very long-chain molecules aluminum connections. This also creates an aluminum, i. H. with about 30 to 60 carbon separation of the olefins by filtration or 65 atoms and more. As a secondary centrifugation possible. Such an upgrading of the product will also result in olefins, their quantity However, the boiling point of the organoaluminum compound can be limited if the reaction can be carried out the introduction of dialkyl temperatures does not increase significantly above 150.degree.

Compared to the prior art, this process modification according to the invention has a number of features of advantages. The aluminum compounds obtained are similar to the real aluminum trialkyls valuable intermediate products for the manufacture of a number of other substances.

A particular advantage of the build-up reaction according to the invention is that the starting materials, z. B. Dialkylaluminum compounds, with a suitable choice of X are much better to handle than the corresponding aluminum trialkyls. For example, aluminum triethyl is highly self-igniting, on the other hand shows the connection

C ₄ H ₉ OA1 (C ₂ H ₅ ) ₂

this property no longer. The connections can can be used as intermediates.

Another advantage of the build-up reaction according to the invention can be seen in the fact that in the known Build-up reaction from aluminum triethyl the ao reaction proceeds only at a very moderate rate. The space-time yield is not very high at the usual test temperatures of 100 to 120.degree great. If you try to increase the temperature, this can lead to explosive degeneration on the one hand lead, in the course of which the injected ethylene largely breaks down into carbon and hydrogen. At higher temperatures, the olefin elimination takes on a greater extent, and so do the reaction products then contain considerable amounts of α-olefins. These α-olefins are then already at relatively high temperatures together with aluminum alkyls and are dimerized in a known manner, so that the normal build-up reaction of aluminum triethyl with ethylene, if you use them at temperatures wants to perform well above 120 ° C, no longer leads to uniformly straight-chain fabrics; the branched dimeric olefins formed at the same time interfere considerably.

On the other hand, if you take an aluminum _{compound of the type R 2} AlYX and add z. B. with a little aluminum trialkyl as a catalyst, the reaction rate in the reaction with ethylene goes down even further, of course, since only the small proportion of aluminum trialkyl is rate-determining for this addition reaction. This reduction can now be safely compensated or overcompensated for by increasing the temperature accordingly, because most of the aluminum _{compounds formed in the reactor continue to be in the form of the R 2} AlYX type which is indifferent to olefins. Even if olefin is split off, only small amounts of the true aluminum trialkyls used as catalysts are found, so the dimerization cannot take on large dimensions.

example 1

298 g of monoethoxy-di-n-octylaluminum are poured into an autoclave flushed with nitrogen, into which 11 air-free liquid dry propylene is then injected. The mixture does not change over many days and months, which is easy to convince by occasional sampling. A catalyst mixture is then prepared by carefully introducing 1 g of nickel acetylacetonate, slurried in 20 ecm of hexane in 20 g of aluminum tripropyl, and using a suitable device to press the deep black-brown mixture into the autoclave. Is allowed to continue at room temperature the autoclave or heated slightly to 30 to 4O ⁰ C, so they are put in samples taken soon realized that changes play in the mixture. The samples are to be carefully pulled out of the liquid phase via a valve through a capillary directly in a nitrogen-filled and cooled to -8O ⁰ C vessel. After the propylene has been expelled rapidly at the lowest possible temperatures, it is decomposed by adding methanol. Propane escapes as a sign that propyl groups bonded to aluminum have formed, and a ^ -hydrocarbon is obtained which contains octane and octene (1). In the course of such a series of experiments, the amounts of propane and octene (1) increase and the octane almost completely disappears. The equilibrium has finally been reached

C ₂ H ₅ O Al (C ₈ H ₁₇ ) ₂ + 2 C ₃ H ₆ : £ C ₂ H ₅ O Al (C ₃ H.) ₂ + 2 C ₈ H ₁₆

discontinued because of the large excess of propylene used far to the right. This state is reached after a few hours.

If the contents of the autoclave are now filled and the propylene is allowed to boil off under nitrogen, the The process goes back again, and with the disappearance of the last propylene one has again exclusively Ethoxydioctylaluminum next to some aluminum tripropyl.

If you want to win ethoxydipropylaluminum in addition to octene (I), you add 16 g of dry, alcohol-free aluminum ethylate to the mixture immediately after filling and mix well. Then the equilibrium is no longer shifted back and the propylene can be distilled off without further ado. Distillation of the residue from a 100 ^° C. bath in vacuo yields about 100 g (90% of theory) of n-octene (l) as the distillate. The residue, which Äthoxydipropylaluminium, boils at 0.5 Torr at 95 ⁰ C. It is a colorless liquid.

The starting material for this test can be readily prepared by brief heating of 244 g with 54 g AIuminiumtrioctyl Aluminiumäthylat to 100 ⁰ C until completely homogeneous dissolution of the Äthylats.

Example 2

172 g Methoxyaluminiumdiisobutyl (prepared by cautious addition of 32 g of anhydrous methanol to 142 g Aluminiumdiisobutylhydrid under nitrogen) are mixed with 500 g of 2-ethyl-hexene (l), under nitrogen, then refluxed (12O ⁰ C). Even after many hours of cooking, no gas has evolved. Finally, small portions of about 2 ecm aluminum triisooctyl each are added through the reflux condenser. After the first servings nothing changes as the methoxyaluminum diisobutyl tends to contain a little of a dialkoxy product through autoxidation, through which the aluminum triisooctyl is decomposed.

209 520/463

From a certain addition onwards, isobutylene begins to develop, the rate of which can be increased with a few more additions and brought to a comfortably manageable level. Quantities between 10 and 30 g have proven to be expedient. Under the circumstances, 5 to 7 hours will suffice to drive off the correct amount of isobutylene. The isobutylene is condensed in a trap cooled ^{to -8O 0 C.} A total of 100 to HOg is obtained.

Then distilling the 2-Äthylhexen used in excess in a vacuum at a maximum bath temperature of 100 ⁰ C and then distilled in the Methoxydiisooctylaluminium high vacuum as possible. Colorless oil, bp mm 180 ⁰ C at 10 ~ ² to 10. ³ Found: Al 9.5 "Λ"; calcd for CH ₃ O Al (C ₈ H ₁₇ ) ₂ Al: 9.7.

Example 3

60 grams of cyclohexyloxyaluminum di-n-hexyl

CH ₂ - CH ₂ .
H ₂ Cf; CH-O-A1 (C ₆ H ₁₃ ) ₂

CH ₂ - CH ₂

(produced by combining aluminum tri-n-hexyl and aluminum cyclohexylate in a molar ratio of 2: 1) are heated to 150 ° C. in a cylindrical glass vessel with an internal diameter of about 3 cm. circulates dry and air-free propylene using a glass frit. Absorbed propylene is continuously replenished. The exiting propylene stream passes two cold traps which are cooled to 0 and -23 ° C. Initially, no reaction whatsoever (and no absorption of propylene) can be observed. After the addition of 2 g of aluminum trihexyl, the elimination of hexene begins. The hexening preferably accumulates in the second cold trap. In the first, some aluminum tripropyl condenses, which is returned to the reaction vessel from time to time. Finally, 30 g of hexene (I) are obtained in the second receiver and 42 g of cyclohexyloxydipropylaluminum in the reaction vessel. This is a colorless viscous oil. Calculated Al 12.9; found 12.6. The experiment takes about 10 hours. The temperature is raised to 200 ⁰ C, the witches elimination is complete after 1 hour. The hexene (1) then contains about Lö ^fl / o hexene (2). If ethylene is used instead of propylene, the amount of hexene is reduced to 25 g, and 5 to 6 g of n-octene are still formed. 33 g of cyclohexyloxydiethylaluminum remain in the reaction vessel.

Example 4

214 g of butyloxydibutylaluminum are mixed with 20 g of aluminum tributyl and heated to 170.degree. At this temperature the steam of octene (1) is introduced, which is brought to the boil in a special vessel. The vapor passing through is condensed into a receiver ^{via a descending cooler kept at around 40 ° C.} Immediately after start of the test escapes from the template butene- (l), which is collected in a second cooled at -8O ⁰ C Template. 2000 g of octene are distilled through the apparatus in the course of about 2 hours, residues of dissolved butene are driven out of the condensed octene (I) by brief refluxing and the octene is returned to the steam generator. After two or three repetitions, butene no longer evolves and the butyloxydibutylaluminum has converted into 326 g of butyloxydin-octylaluminum mixed with 36 g of aluminum trioctyl. To produce a completely uniform product, 12.3 g of aluminum butylate can be added and the aluminum trioctyl can also be converted into butyloxy-di-n-octylaluminum.

Example 5

114 g of aluminum triethyl are added very carefully under nitrogen and with cooling with a mixture of 60 g of completely anhydrous n-propyl alcohol and 300 ecm of η-hexane, ethane developing in a vigorous reaction and monopropoxydiethylaluminum being formed. The hexane is then distilled off and about four fifths of the liquid residue is poured into an autoclave with a capacity of 1000 ecm, previously flushed with nitrogen, onto which 112 g of dry and oxygen-free ethylene are then pressed. If it is now heated to 140 to 150 ° C. while shaking, a pressure of about 200 atm is established, which however remains constant for hours. There is no ethylene absorption. The mixture is allowed to cool and a mixture of the remaining fifth of propoxydiethylaluminum and 8 g of diethylaluminum hydride is then injected using a small liquid injection pump. If one now warms up again while shaking, one observes a clear pressure drop from about 120 ° C. At 130 ⁰ C, the uptake of ethylene is fast, and after 6 to 7 hours, the maximum pressure of about 200 to 20 is energized at.

It is allowed to cool, the residual pressure is blown off and the liquid contents of the autoclave are filled under nitrogen. A few grams of liquid olefins, essentially a mixture of n-hexene (I) and n-octene (I), can be drawn off from this by heating in vacuo to 100 to 120 ° C. The remaining liquid reaction product has an aluminum ^{content of about 11 fl} / o and consists of a mixture of higher propoxyaluminum dialkyls of average composition

One can easily show this by hydrolysis. This gives a reaction product which is insoluble in water and which, after having added the n-propanol Water has completely washed out, only from paraffins with at most a few percent straight-chain Consists of olefins. Fine distillation with a spinning band column gives

Hexane 43 g

Dodecane Ed

Octane 36.5 g

Tetradecane 4 g

Decane 23 g

The examples 5 compiled in the following table are based on the pattern of this example 4 up to 12 have been carried out with the only

decided that the catalyst was added from the beginning. The work-up by hydrolysis at the end with the formation of paraffins and the substances of the general formula XYH was only carried out to prove the course of the reaction. The work-up is somewhat different depending on the nature of the XYH. If the XYH is noticeably acidic (e.g. if XYH is a phenol, thiophenol, or mercaptan),

so is washed with alkali, XYH is a lower one Alcohol, it is extracted with water. If XYH is an alcohol that is only sparingly soluble in water, then treated with aqueous methanol. With high-boiling XYH, the paraffins are simply distilled away. Special work-up methods required in individual cases are listed in the last column of the Table briefly given.

Aluminum connection catalyst Ethylene Tempe Ver Coals
hydrogen C ₂₄ Kind of on game the AnX-Y-AlR ₂ , lot rature duration from hydrolysis up to C ₃₈ = 500 g processing after Formula and amount G ⁰ C (ClA \ Amount and too (not separated) of hydrolysis 6th Al (C ₄ He) ₃ composition C ₃ = 29.4 g CH ₃ S-Al (C ₈ H ₁₇ ), 5 g (n) C ₈ = 10g C ₅ = 49g Alkaline wash 300 g (n) ^ 168 140 10 Ci ₀ = 38 g
/ - * - jr \ _ C ₇ = 32g Ci ₄ = 79 g C ₉ = 14g Ci ₆ = 69 g C ₁₁ = 4.5 g C ₁₈ and 7th AlH ₃ higher = 87 g C ₂ = 3.6 g (CH ₃ ) ₃ C-O-Al (C ₅ Hn) ₂ 2g C ₅ = 16g C ₄ **) = 135 g Wash with 242 g (n) 112 150 2 C ₇ = 49g
C ₉ = 64g
C ₁₁ = 50g C ₆ = 37g water C ₁₃ = 30 g C ₈ = 46.8 g C ₁₅ = 13 g C ₁₀ = 44.2 g C ₁₇ = 5g C ₁₂ = 23.8 g besides a few Ci ₄ = 11.9 g ° / o even Ci ₈ = 7.3 g 8th Al / CH ₂ \ Ci ₈ = 9g C ₁₈ = 2g C ₆ H ₅ -CH ₂ -O-Al (Ci ₈ H ₃ T) ₂ I ί ^ Τ-Γ Γ H I C ₂₀ = 59 g Ci ₂ = 3 g Distillation in 566 g (n) I CW-C ₃ M ₇ I. 224 130 20th C ₂₂ = 78 g Ci ₄ = 7g Vacuum, ben \ CH, / 3 Ci ₆ = 16g
Ci ₈ = 20 g cyl alcohol bil 20 g up to C ₃₀ = 400 g det forward AI (C ₃ Ht) ₃ and 295 g 9 10 g Residue TJ TJ
Xl ₂ rl ₂ C ₃₂ to about C ₄₄ ) Distillation, I I yy 56 160 1 C ₂ = 4.8 g Hexahydro YY ₀ / \ ^ - C ₄ = 22.1g phenylethyl N - / ^ CHo C ₈ = 38.8 g alcohol remains M j - Al (C ₄ Hg) ₃ C ₈ = 42.2 g in arrears 10 240 g ^{Ha Ha} CH ₂ - O - Al (C ₃ Ht) ₂ 18 g (iso) C ₁₀ = 31.2g C ₆ H ₅ -S-Al (C ₄ Hg) ₂ C ₁₂ = 22 g Alkaline wash 250 g (iso) 280 *) 125 30th Ci ₄ = 10.5 g C ₁₆ = 5.2 g Ci ₈ = 2g AlH (C ₄ Hg) ₂ 11 ig CH ₃ Alkaline wash 560 170 3 ( / -0-Al (C ₁₂ H ₂ S) ₂ CH ₃ 486 g Al (C ₂ Hg) ₃ 12th 30 g C ₁₂ H ₂₅ -S-Al (C ₂ Hs) ₂ Distillation, 286 g 140 90 40 Alkaline wash

*) Only 210 g of this used.
**) This fraction contains 120 g of isobutylene.

15 16

Example 13 and mixed it with that obtained according to a)

(Higher α-olefins from ethylene) reaction product. You pump up the liquid

a trickle tower provided with full bodies, with

a) A pressure-resistant and with a liquid heating ethylene of 20 to 100 at pressure is filled. The refrigeration system or surrounded steel pipe of 20 m 5 temperature is maintained at 20 to 4O ⁰ C. One length with 3 cm clear width (or one can also use the trick mentioned in the German patent corresponding number of copper capillary connections 1001981 and add an acetylene hydrocarbon to shorter steel pipes connected in series). This is usually not necessary in sections of 20 cm in length with built-in components. The reaction can be provided according to the drawing, so that it is subdivided into a total of io, firstly, by the ethylene absorption in the tower, a hundred small individual sections. That (the pressure is kept constant, the fed pipe is ^{heated to 100 0} C and measured with ethylene from ethylene), secondly, the amount of the filled at 100 atm pressure. At the end, the ethylene is expanded to about 10 atm in the hydrolysis of samples from a template running down below, and ethane is developed from here. The reaction is fed into a compressor, which ends in the cycle with 15 when 2 mol of ethane ge-100 at per atom of aluminum is released back to the inlet of the pressure pipe. forms are. If necessary, the product is repeated. This inlet of the reactor is then pressed onto the tower.

through a second line by means of a heated c) The correctly converted product is now with

Liquid injection pump mixed with molten phenoxy 3.1 kg of dry aluminum phenolate and diethylaluminum, which distills 1% aluminum triethyl 20 - expediently immediately in a vacuum. One contains. The first stage of the compressor can receive to-472 kg of a mixture of olefins to Siedesätzlich ethylene are fed to the appropriate point 110 ° C (10- ³ Torr). The residue remains cold with aluminum triethyl or 498 kg of phenoxydiethylaluminum at a pressure of about 10 atm. The nickel flocculates molten phenoxydiethylaluminum washed from the distillation and can be obtained by filtration. The incoming ethylene should not be recovered as much as possible. The organoaluminum product is oxygen, no moisture, no CO ₂ , no boiling at 120 ^° C. (10 ^-3 Torr). After renewed it can contain acetylene and no sulfur compounds. Addition of aluminum triethyl to the process. At first, no fresh ethylene is allowed to be recycled.

enter the apparatus. To the extent that the olefin mixture obtained is distilled

If the reactor fills with liquid, the pressure changes. 30 of a column filled with wire spirals (height 4 m, it is kept constant at about 100 atm. If the Re diameter is 8 cm). In addition to approximately 34 kg of the actuator, the temperature is increased, but the temperature is increased
is (absorption of ethylene). You regulate them
Temperature so that the pressure decrease is about 35
4 bpm amounts to. To do this, a temperature of
much more than 150 ⁰ C necessary, so must the
Phenoxydiäthylaluminium a little more aluminum triethyl can be added. With this size of the
Ethylene absorption can cause uncomfortable warmth
Avoid jams safely. You have this point

reached, the ethylene pressure is maintained by example 14

carry fresh ethylene into the system constantly

to about 100 at and sets the injection pump for the one proceeds in the first stage, as in example 13

liquid aluminum compound on such a gel 45 described. In the second stage you ask, as there speed that the one described at the end of the apparatus under b) produces a fine nickel suspension on the template below to be deducted aluminum and mixes this in a pressure vessel with the bond has an aluminum content that flüswunschten the reaction product obtained from a) and 3000 kg corresponds to mean molecular weight. sigen propylene. After about 5 hours, this has been If you drive the apparatus, starting with a relatively high 50, new equilibrium is set. One slips into the Injection speed, which is later reduced, so reactor 3.1 kg of dry aluminum phenolate and if the liquid reaction product is initially still stirred, the mixture is stirred very well for about 1 hour. a lot of starting material, and this must then be the input be fed back. Finally, continue according to Example 13. In addition to 465 kg of olefins but the arrangement works perfectly evenly. At- 55 from the boiling point 63 ° C / 760 Torr to 150 ° C / 12 Torr for example, at an injection rate, phenoxydipropylaluminum is now obtained as high from 3 kg / hour and at 152 ° C the absorption boiling residue.

speed of ethylene 3 kg / hour, and this modification of Example 13 is important

liquid reaction product had a constant aluminum if one considers the synthesis of even-numbered olefins minimum content of 7.5 ° / o. In this way, 60 of the odd-numbered olefins were attempted to pass over. That too Finally, from 500 kg of phenoxydiethylaluminum, the reverse is easily possible in that one in kg of phenoxydialkylaluminum with a through-stage 1 that uses phenoxydipropylaluminum and obtained average carbon number 10 of the alkyl groups. in stage 2 again ethylene.

b) You introduce yourself by carefully entering. -I ₁ ^

g finely powdered Ni acetylacetonate in 400 ecm 65 Example 15

Hexane and 500 ecm aluminum triethyl under stick- Man proceeds as in the previous example

substance wrote a solution or suspension of colloidal, but goes from Monomethoxydiäthylalu- or finely divided nickel in aluminum triethyl her minium, activated by aluminum triethyl. off and

80 kgHex- (l) Sdp. 63 ° C / 760 Torr 101 kg octene (l) Sdp. 122 ° C / 760 Torr 98 kg decen- (l) Sdp. 60 ° C / 12 Torr 69 kg dodecene (l) Sdp. 88 ° C / 12 Torr 35.5 kg tetradecen- (l) Sdp. 122 ° C / 12 Torr 20.5 kg hexadecen- (l) Sdp. 150 ° C / 12 Torr

adjusts the reaction in the reactor to a final aluminum content of 4%. The first reaction product is fixed partially, it must, therefore, in the second stage at a somewhat higher temperature - be worked - 60 to 7O ⁰ C. During the distillation in the third stage, the aluminum compound now goes

CH ₃ OAl (C ₂ Hj) ₁ ,

together with the lower proportion of olefins as a first run at 110 ° C / 10 Torr above. She lets herself into this Use the shape again. However, one can also cook the olefins with their equivalent Amount of aluminum triisobutyl or diisobutyl hydride in toluene into the corresponding aluminum trialkyls transfer, of which the methoxydiethylaluminum is smooth by a second distillation lets separate.

The majority of the olefinic reaction products remain in the residue during the first distillation. It is expediently obtained in pure form by distillation in a high vacuum. From 1000 kg of reaction product from stage 1, 480 kg of these olefins, which _{comprise the molecular range from about C 14} to C ₃₀ , are obtained.

Example 16

A pressure-resistant steel pipe with a clear width of 1 cm and a length of 6 m has become a vertical helix with a diameter of 20 cm and a height of 1 m and surrounded by a special vessel with a suitable heat transfer fluid (e.g. a mixture of diphenyl and diphenyl oxide) is. It is heated to 200 ° C. At the upper end of the lower third of the turned tube can Ethylene can be supplied laterally through a capillary. Ethoxydiethylaluminum is pumped from below, which contains 1 to a maximum of 2% aluminum triethyl, into the tube and leaves one at the same time Enter a stream of ethylene of 10 atm through the lateral capillary. In the lower third of the system, the Aluminum compound heated to 200 ° C. Then it reacts with the ethylene and becomes at the same time driven rapidly through the upper two thirds of the helix by the stream of ethylene. Escaping Ethylene and reaction product are quickly cooled and fed to a template, from which one Above the ethylene, below the liquid reaction product can withdraw. The ethylene is in the cycle recycled, although it was previously carried out in a known manner from entrained butylene and hexene is to be freed by suitable cooling, washing or by absorption charcoal. One puts the Pump in so that the ethylene-liquid contact time is between 1 and 10 minutes, the ethylene flow is about ten to twenty times measured on the volume of compressed ethylene from the liquid stream.

The liquid reaction product consists of a mixture of olefins (predominantly with the group = CH ₂ at the end, as can be easily seen from the infrared spectrum) with higher homologues of the ethoxydiethylaluminum used, which can be proven most easily by hydrolysing the total mixture and examining the hydrocarbons formed . There are obtained (in addition to ethyl alcohol) hexene + hexane, octene + octane, decene + decane and higher hydrocarbons. The paraffins correspond to the alkylene originally bound to aluminum.
The ethylene for this experiment must be very pure.

Example 17

30 g of aluminum tribenzyl are mixed with 11.5 g under nitrogen (just the right amount would be 12.3 g) aluminum tri-sec-butylate previously carefully distilled in vacuo

Al (O-CH (CH ₃₎ C ₂ H _{5) 3}

added and reacted in an autoclave of 200 ecm content under the conditions of Example 5 with 17 g of ethylene. A liquid reaction mixture containing 4.7% aluminum is obtained. That there is essentially a homologous aluminum compound of the average composition C ₄ H ₉ -O-A1 [(C ₂ H ₄ ) ₂ CH ₂ -C ₆ H ₆ I ₂ sec.

must be present can easily be determined by hydrolysis. This gives 45 g of oily reaction product, which breaks down into the following fractions during distillation:

sec. Butanol toluene 1-phenylpropane l-phenylpentane 1-phenylheptane Bp 99 ° C
4g Bp 111 ° C
8.3 g Bp 55 ° C / 20 torr
7g Bp 85 ° C / 20 torr
3g Bp 120 ° C / 20 torr
2g

Example 18

354 g of the aluminum trialkyl from 1-vinylcyclohexene (3) from the formula:

HC

CH ₂

HC,

- C JHU

/ V ' \ s JlI2 ν.' JtTg

Al

(manufactured according to German patent specification 917006)

are mixed with 500 ecm dry and air-free toluene under nitrogen. Dripping into the mixture while stirring vigorously 31g of previously completely dehydrated and freshly distilled in vacuo ethylene glycol a. The glycol dissolves with the development of heat. If everything has become homogeneous, then distilled one toluene together with 110 g of 1-ethylcyclohexene (3), finally in a vacuum. 5 g of aluminum triethyl are added to the thick oily residue and transfer the mixture to a 1-1 autoclave under nitrogen. 112 g of ethylene are injected and otherwise treated according to Example 5 further. The finally obtained liquid autoclave contents are treated according to Example 1 with 11 liquid propylene in the presence of colloidal nickel and aluminum tripropyl Further. Finally, one carries per molecule of the real one present in the mixture Aluminum trialkyls 0.75 mol of anhydrous glycol and then allows the propylene to boil off. The residue

209 520/463

can be smoothly obtained by distillation in vacuo in 280 g of a hydrocarbon mixture with a boiling range of 70 ° C / 20 Torr to 160 ° C / 0.5 Torr and a non-distillable residue of the compound (C ₃ H ₇ ) ,, Al — O — CH ₂ - CH ₂ - O - Al (C ₃ H ₇ ),

separate. The infrared spectrum of the distillate suggests that terminal vinyl groups and Cyclohexenyl radicals are present in the same number. The distillate certainly consists of a mixture of some homologous diolefins of the formula

HC CH ₂

. CH - (C ₂ H ₄ ) "- CH = CH ₂

CH ₂ - CH ₂

η - 1, 2, 3 and higher.

Claims (12)

PATENT CLAIMS: 1. A process for converting oxygen or sulfur-containing organoaluminum compounds into oxygen or sulfur-containing aluminum compounds which contain other hydrocarbon radicals, optionally with the production of olefins, characterized in that organoaluminum compounds of the general formula are used XW [Y-AlR ₂ J _n in which X is any monovalent or polyvalent hydrocarbon radical, η is the valency of the Radicals X, Y oxygen or sulfur and R any hydrocarbon radical which is at the carbon atoms connected to the aluminum does not contain any unsaturated bonds, means, with olefins in the presence of aluminum compounds, the three valences Contain carbon bonded, or from dialkylaluminum hydrides or from aluminum hydride as catalysts. 2. The method according to claim 1, characterized in that the radical X-Y in the organoaluminum Starting compounds the remainder of any alcohol, phenol, naphthol, or their derivatives substituted by alkyls in the benzene nucleus. 3. Process according to Claims 1 and 2, characterized in that there is a connection XAl (C ₂ H ₅ ), Reacts with ethylene. 4. Process according to Claims 1 to 3, characterized in that there is a compound the general formula 55 with ethylene, at pressures above 10 at and preferably at temperatures between 120 and 150 ° C, converts, with essentially higher homologues of the compound XW [Y-AlRJ ₁₁ can be obtained. 5. The method according to claim 4, characterized in that that by increasing the reaction temperature splits off olefins above 170 ° C. 6. Process according to Claims 1 and 2, characterized in that there are aluminum compounds the general formula XW [Y-AlRJ _n used, in which at least one radical R is a radical higher than C ₂ H ₅ , and this with ethylene, under normal pressure, reacts, in addition to a lower or higher homologue of the starting material, an olefin other than ethylene is obtained. 7. Process according to Claims 1 to 3, characterized in that one first consists of an aluminum compound the general formula and ethylene builds up a higher aluminum compound, then in the presence of nickel, preferably colloidal nickel, further treated with ethylene or with a monoalkylethylene, and the reaction mixture of little real aluminum trialkyls, larger amounts of a compound the general formula XYA1 (C ₂ H ₅ ) ₂ or XYAl (CH ₂ -CH ₂ R) ₂ and olefins of the general formula H ₂ C = CH (C ₂ Hj) _n-1 C ₂ H ₅ in which η means any integer, separates by distillation. 8. The method according to claims 3 to 7, characterized in that one by variation the amount of ethylene added determines the composition of the end product. 9. The method according to claims 5 to 8, characterized characterized in that compounds of the general formula are used as starting materials with such a substituent X selects that the boiling point of these compounds is higher than the boiling point of the highest boiling olefin or lower than the boiling point of the lowest boiling point Olefins. 10. Process according to Claims 1 and 5 to 7, characterized in that one is used as the olefin higher olefin than ethylene is used, which optionally does not correspond to one R of the organoaluminum starting compound, one being in addition to a lower or higher homologue of the starting compound XW [Y-AlR ₂ ], the olefin corresponding to the radical R is obtained. 11. Process according to Claims 1 to 10, characterized in that the aluminum compound is used which contains three valences bonded to carbon, aluminum trialkyls, preferably in amounts of 1 to 5% of the compound XW [Y- AlRJ _n begins. 12. The method according to claims 1 to 11, characterized in that there is in the end product the proportion of catalyst by adding compounds that only react with one AlC valence, destroyed. 1 sheet of drawings © 209 520/463 3.62